Diazo derivatives and process for their preparation

Details Diazo derivatives and process for their preparation Diazo derivatives and process for their preparation

2002-07-03

2004-05-25

Powers, Fiona T. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Diazo or diazonium

C534S558000, C534S565000, C546S247000, C544S168000, C560S159000, C162S160000, C422S040000

Reexamination Certificate

active

06740741

ABSTRACT:

FIELD OF THE INVENTION
The present invention concerns novel diazo derivatives of general formula (I) hereafter reported, the process for their preparation and their use as deacidifying agents in the deacidification treatment of paper.
STATE OF THE ART
It is universally acknowledged that one of the causes of the too rapid deterioration of cultural materials on paper is the presence of acidity in the material. p In modern paper, acidity is usually caused during the manufacture in the paper factory; however, acidity can often be found even in papers or books that are made from acid-free paper, as it comes from some types of ink for manuscripts, that was widely used in the past.
Experts agree that in order to prolong the life of books and documents that are stored in libraries and archives (according to the experts from three to five times as much) it is necessary to eliminate the acidity from the materials, by using a technique that in the specialised environment is known as “deacidification”. Obviously, in order to avoid the errors committed in the past, new documents and books to be stored should be made with acid-free paper (UNI n. 10332—Paper for documents. Requirements for the maximum duration and durability and UNI n. 10333—Paper for documents. Requirements for duration).
In the Italian public libraries there are currently 30 million books; an equal amount of paper documents are kept in public archives.
From fragmentary surveys carried out in some Italian preservation environments, in agreement with similar research carried out abroad on a wider scale, it has been found that 20-30% of library and archive materials are now so fragile that they cannot be made available for free consultation; the risk of further damage would be too high. Alongside this relatively low percentage however, it has been found that 60-80% of preserved books and documents need to be deacidified or in some way stabilised; otherwise, it would only be a matter of time before all the acid material would become fragile, and no longer consultable.
In view of what above said, it is evident that, in order to protect the Italian book and document heritage, it is necessary to be able to intervene with mass deacidification techniques, or however, with stabilisation techniques that would slow down deterioration; these would be techniques that allow the entire heritage to be restored in a time span of no more than ten, fifteen years.
It is therefore much felt the need for products that allow effective and persistent deacidification of paper, without secondary effects on the material treated.
SUMMARY
The Applicant has now found novel diazo derivatives of general formula (I) that are effective as deacidifying agents in the deacidification treatment of paper, without showing the drawbacks of the deacidification methods that have been used so far, and a process for their preparation.
Therefore subject of the present invention are the diazo derivatives of general formula (I)
wherein R′ is chosen from H and methyl, and R is the group
where n=1, 2, 3, 4, 5; and R
1
and R
2
, equal to one another, are chosen between methyl and ethyl, or R
1
and R
2
, taken together, form with N a piperidine ring or a 4-morpholine ring;
provided that, when n=2 and R′=H, R
1
and R
2
are different from methyl.
Further subject of the invention is the process for the preparation of the diazo derivatives of general formula (I)
wherein R′ is chosen from H and methyl, and R is the group
where n=1, 2, 3, 4, 5; and R
1
and R
2
, equal to one another, are chosen between methyl and ethyl, or R
1
and R
2
, taken together, form with N a piperidine ring or a 4-morpholine ring;
comprising the following steps:
a) reaction between the amine of formula (II) and ethyl chlorocarbonate of formula (III) to obtain carbamate (IV)
 in which R is defined as above;
b) nitrosation of the carbamate (IV) obtained from the step a) to obtain N-nitroso-carbamate of formula (V):
 wherein R is defined as above;
c) reduction of the N-nitroso-carbamate (V) obtained from step b) to obtain the desired formula (I) compound:
 wherein R and R′ are defined as above.
Further subjects of this invention are the formula (IV) compounds and their N-nitroso derivatives of formula (V); and the use of the formula (I) compounds in the deacidification methods of paper material.
DETAILED DESCRIPTION OF THE INVENTION
According to a particular embodiment of the present invention, step a) of the present process is carried out at room temperature using CH
2
Cl
2
as a solvent, and with a large excess of K
2
CO
3
so as to completely neutralise the HCl that forms during the,reaction; the preferred stoichiometric ratio between amine (II), K
2
CO
3
and ethyl chlorocarbonate (III) is 1:4:3.
The reaction in step b) of the present process can be carried out at a temperature of 1-2° C. using HCl/NaNO
2
as reagent. A large excess of HCl/NaNO
2
is preferably used so as to achieve complete nitrosation of the formula (IV) product.
According to a particular embodiment of the invention, step c) of the present process is carried out at a temperature of 1-2° C. with a solution of sodium methoxide in methanol. By using a slight excess of sodium methoxide compared to the amount of the formula (V) compound, the formula (I) compound is obtained in which R′ is H, whereas with a large excess of sodium methoxide, the compound (I) is obtained in which R′ is methyl. Methanol, ethanol and Na
2
CO
3
are obtained as the only secondary reaction products.
The so obtained product is dissolved in a suitable inert stabilising solvent, preferably in diethyl ether, and the ether solution of the products is kept at a temperature of −18° C. and away from light, and it is used in this form without isolating the product.
The formula (I) compounds can be used for the deacidification of paper products according to techniques known in the art; preferably, these compounds can be used in mass deacidification techniques, where “mass deacidification techniques” means the technique described in the copending patent application in the name of the same Applicant, wherein an increase in the pH up to 9-10 of the paper material treated is obtained, and such an increase persists in time for at least 6 months. Following the treatment with compounds of general formula (I) prepared with the present process, no undesired side effects were noted, such as the formation of unpleasant odours or colouring caused by the treatment itself.
The present compound of formula (I) wherein R′ is H and R is the group
where n=1, and R
1
and R
2
, taken together, from with N a piperidine ring, has proved to be especially effective in obtaining a prolonged continuation of the basic pH obtained by the deacidification treatment.
The following examples are given to provide non-limiting illustrations of the present invention.


REFERENCES:
patent: 3163536 (1964-12-01), Nishio et al.
patent: 3513241 (1970-05-01), Hoyer et al.
patent: 1155328 (1963-03-01), None
patent: 2313012 (1974-10-01), None
patent: 2528496 (1976-01-01), None
patent: 0545180 (1993-09-01), None
patent: 1273707 (2003-08-01), None
patent: WO-97/29097 (1979-08-01), None
Pecher et al., Chemical Abstracts, 53:3088, 1959.*
Rav-Acha et al., Chemical Abstracts, 111:96377, 1989.*
Ch. Rav-Acha, “The Catalytic Effect of Cationic Amino Micelles on the Hydrolysis of Substituted Phenyl Esters”,Tetrahedron, vol. 44, No. 18, pp. 5879 to 5892, (1988).
Pecher et al., “Aminoethylurees, Aminoethylthiourees ET Aminoethylurethannes Substitues, Et Leur Action Sur La Filariose”,Bull Soc. Chim. Belg, 66, pp. 545-564, (1957).
Buckley et al., “Decomposition of Aliphatic Diazo-Compounds, by Trimethyl Borate:The Preparation ofBranched-Chain Paraffins of High Molecular Weight”,Chemical Society, pp. 3701-3704 (1952).
Abstract of South African Patent 6706747, Nov. 8, 1968.

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